GB2032638A

GB2032638A - Silver photographic material containing yellow coupler

Info

Publication number: GB2032638A
Application number: GB7931576A
Authority: GB
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1978-09-13
Filing date: 1979-09-12
Publication date: 1980-05-08
Also published as: JPS5946384B2; GB2032638B; US4266019A; JPS5538576A; DE2936842A1

Description

1

GB 2 032 638 A 1

SPECIFICATION

Silver photographic material containing Yellow coupler

This invention relates to couplers which provide, upon coupling reaction with the oxidation product of a primary amine developing agent, a yellow dye having an extremel.v excellent fastness.

5 In the field of color light-sensitive materials, it has been eagerly desired to keep the image in its 5 '

developed state over a long period of time. To enhance fastness of a dye formed from a coupler is the most fundamental approach to this object. Unlike cyan couplers and magenta couplers, yellow couplers (i.e. couplers which form a yellow dye) do not provide a dye having improved fastness even when used together with so-called anti-fading agents, but rather provide reduced fastness. Therefore, with respect 10 to yellow couplers it has been particularly desired to enhance the fastness of the dye formed from the 10 couplers.

Japanese Patent Publication No. 16,058/74 and U.S. Patent 3,892,576 each disclose couplers having a structure which might be considered analogous to that of the yellow couplers of the present invention represented by formula (I) below.

15 The former publication discloses pyrazolone magenta couplers having a 15

—NHCOCH

\

R2

moiety where R, and R2 represent alkyl groups. The invention disclosed therein is directed to reducing the amount of solvent required to incorporate the couplers into a color photographic emulsion and improve the spectral absorption characteristics of color images by utilizing the high solubility of the 20 couplers in high boiling organic solvents, and differs from the present invention in construction and 20 object. In addition, yellow couplers show a different behavior from magenta couplers in terms of their photographic properties, and while magenta couplers having a

/Rl

—NHCOCH

\

R2

moiety show a high solubility for high boiling organic solvents, it is extremely difficult to predict that . 25 yellow couplers having such a moiety would provide extremely fast dyes. 25

U.S. Patent 3,892,576 discloses introducing a

—NHCO—CH,—CH

\

r,

moiety into photographic additives to increase their diffusion-resistance.

A principal object of the present invention is to provide photographic materials containing yellow 30 couplers which provide, by coupling reaction, a dye having good light fastness, without sacrificing other 30 photographic properties to attain this object.

In addition to the above-described light fastness, the couplers used in the present invention show an excellent solubility in high-boiling organic solvents and an excellent color-forming property.

The couplers used in the present invention are represented by formula (I):

/Rl

A—NHC —CH (I)

35 0 ^Rj 35

wherein A represents a yellow coupler nucleus from which one hydrogen atom bound to a carbon atom other than at the coupling active position is removed, and R, and R2 each represents a straight or branched alkyl group containing 2 to 16 carbon atoms, with the sum of the carbon atoms contained in R, and R2 being 10 to 20.

2

GB 2 032 638 A 2

Preferably A represents a pivaloylacetanilide coupler nucleus, a benzoylacetanilide coupler nucleus, a malondiamide coupler nucleus, a benzothiazolylacetanilide coupler nucleus, an benzothiazolylacetate coupler nucleus, a benzoxazolylacetamide coupler nucleus, a benzoxazolylacetate coupler nucleus, a benzimidazolylacetamide coupler nucleus, a benzimidazolylacetate coupler nucleus, and those derived 5 from hetero cyclic-substituted acetamides and hetero cyclic-substituted acetates, where such 5

heterocyclic-ring substituent can be a 5-, 6- or 7-membered ring which can contain more than one hetero atom such as a nitrogen atom, an oxygen atom and sulfur atom, as described in U.S. Patent 3,841,880.

Particularly useful groups represented by A are those derived from the compounds represented by 10 the following formula (II); 10

R,—C—CH—C—NHR4

11' 1 11 <m oxo (")

wherein R3 represents an aliphatic group, an aromatic group, or a hetro cyclic group, and R4 represents an aromatic group or a hetero cyclic group and X is defined as below.

In the above formula, the aliphatic group such as an alkyl group, an alkenyl group, an aralkyl group, an 15 alkoxyalkyl group or ari aryloxyalkyl group represented by R3 preferably contains 1 to 22 carbon atoms, 15 and may be substituted, unsubstituted, straight, branched or cyclic and is preferably an alkyl group.

Preferable substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, etc. which themselves may further be substituted. Specific examples of useful aliphatic group represented by R3 are; isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-20 dimethylbutyl, 1,1 -dimethylhexyl, 1,1 -diethylhexyl, dodecyl, hexadecyl, octadecyi, cyclohexyl, 2- 20

methoxyisopropyl, 2-phenoxyisopropyl, 2-p-tert-butylphenoxyisoprapyl, a-aminoisopropyl, a-(diethylamino)isopropyl, a-succinimido)isopropyl, ar-(phthalimido)isopropyl and a-(benzenesulfonamido)isopropyl.

Where R3 or R4 represents an aromatic group such as a phenyl group or a naphthyl group (in 25 particular a phenyl group), the aromatic group may be substituted. An aromatic group such as a phenyl 25 group may be substituted by a group having up to 32 carbon atoms such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an aliphatic amido group, an alkyisulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, etc. The alkyl substituent may contain in its chain an aromatic group such as a phenylene group. The phenyl 30 group may also be substituted by a group having 6 to 32 carbon atoms such as an aryloxy group, an 30 aryloxycarbonyl group, and arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc. The aryl moiety of these substituents may be further substituted by one or more alkyl groups containing a total of 1 to 22 carbon atoms.

Furthermore, the phenyl group represented by R3 or R4 may be substituted by an amino group 35 including a lower alkyl-substituted amino group containing 1 to 6 carbon atoms, a hydroxy group, a 35 carboxy group, a sulfo group, a nitro group, a cyvano group, a thiocyano group, or a halogen atom.

Still further, R3 or R4 may represent a'substituent wherein a phenyl group is condensed with a saturated or unsaturated ring, which may contain hetero atoms, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl 40 group, etc. These substituents themselves may have a substituent or substituents. 40

Where R3 or R4 represents a 5- or 6-membered heterocyclic group containing more than one hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom, which may be saturated, unsaturated or aromatic, the heterocyclic group is bound to the carbon atom of the carbonyl group of the acyl group or to the nitrogen atom of the amido group in the ar-acylacetamido group via one of the 45 ring-forming carbon atoms. Examples of such heterocyclic rings include thiophene, furan, pyran, pyrrole, 45 pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine,

oxazine, etc. These may further have a substituent or substituents on the ring.

X in formula (II) represents a group represented by the following formula (III), (IV) or (V):—

3

GB 2 032 638 A 3

w

0

0 r

(h)

(X>

In general formula (III). Z represents the non-metallic atoms, which may contain an oxygen group or a sulfur group, necessary for completing a 4-, 5- or 6-membered ring, which may be saturated or unsaturated, together with yy0

Suitable examples of the ring represented by general formula (III) are shown as follows.

(k ^0 <L .N. ,0 (L N. J

T (

o.

0

O N. .0

Y

.n

■n H

10

In general formula (IV), R represents a monocyclic aryl group such as a phenyl group having 6 to 30 carbon atoms, which may be unsubstituted or substituted by a group such as —S02CH3, —COOH or 10 —CN, for example.

cooh,

so2ch3

15

4-carboxy phenyl, 4 methanesulfonyl phenyl, 4-cyano-phenyl, etc.; or a 5- or 6- membered hetero cyclic group containing more that one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom which may be saturated or unsaturated, such as pyrazole, triazole, tetrazole, etc. In general formula (V), R5 and R6 each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, the carboxylic acid of which contains 1 to 18 carbon atoms and may be selected from an aliphatic acid group and, as an ester group, a methyl group, an ethyl group, an octyl group, etc.; an amino group, an

15

GB 2 032 638 A

alkyl group having 1 to 18 carbon atoms, which may be straight chain, branched or cyclic, an alkylthio group having 1 to 18 carbon atoms, in which the alkyl moiety may be straight chain, branched or cyclic, an alkoxy group having 1 to 18 carbon atoms, in which the alkyl moiety may be straight chain!

branched or cyclic, an alkylsulfoxy group having 1 to 18 carbon atoms, in which the alkyl moiety may be straight chain, branched or cyclic, a carboxy group, a sulfoxy group, a phenyl group, which may be substituted by a chlorine atom, a methoxy group, a methy group etc., or a hetero cyclic group such as a pyridino group.

Of these, the moieties represented by the following formulae (VI) to (IX) of the formula (III) are preferred:

10

o n. .0

*r r

-n-xa

X2

(3T)

O N. .0

*r r

-w x2

'(M)

°YnY°

X4-N N—x5

(he)

(h)

10

In these formulae, X, and X2 each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, which may be straight chain or branched, a monocyclic aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, which may be straight chain, branched or cyclic, a monocyclic aryloxy group having 6 to 18 carbon atoms, or a hydroxy group. X3, X4 and X5 each 15 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, which may be straight chain 15 or branched, a monocyclic aryl group having 6 to 18 carbon atoms, a monocyclic aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 18 carbon atoms, which may be an aliphatic group or ■ an aromatic group, W represents an oxygen atom or a sulfur atom, X6 represents a monovalent substituent such as a hydrogen atom, a halogen atom, a nitro group, a cyano group, a thiocyano group, 20 a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl group having 1 to 18 20 carbon atoms, which may be straight chain or branched, an alkenyl group having 1 to 18 carbon atoms, which may be straight chain or branched, a monocyclic aryl group having 6 to 20 carbon atoms, an amino group, a carboxy group,- an acyl group, an ajkoxycarbonyl group having 1 to.18 carbon atoms, aryloxycarbonyl group having 6 to 28 carbon atoms, a carbamoyl group having 1 to 18 carbon atoms, 25 an acylamino group, which may be an aliphatic acylamino group having 2 to 18 carbon atoms or an 25 aromatic acylamino group having 7 to 29 carbon atoms, an imido group, a sulfo group, an alkylsulfonyl group having 1 to 18 carbon atoms, an arylsulfonyl group having 6 to 28 carbon atoms, an alkoxysulfonyl group having 1 to 18 carbon atoms, an aryloxysulfonyl group having 6 to 28 carbon atoms, a sulfamoyl group, a sulfonamido group, an ureido group or a thioureido group.

30 A preferred class of couplers within the formula (II), wherein R4 is aryl, are represented by the 30

formula (X):

where Rv R2, R3 and X are defined as in formula (II) and Y is a halogen atom or an alkoxy group. Examples of couplers used in the present invention are as follows:

5

GB 2 032 638 A 5

ch3 ch3

i i

,ch—ch2 —c—ch3

nh-coch' ch3 ru

^ |3

sCH2CH?CH-CH2-C-CH3

1. (ch3)3ccochconh- 1 1 0

^3 3

3.

(ch3)3ccochconh—/ \

(vjlo /

ci nh-coch \

Ws c12»25

CH3-N

oc4 hg

6

GB 2 032 638 A 6

ch3 ch3

,ch—ch2-c— ch^ nh-coch" ch3 ch c¥£)-cochconhh0 CH2C"2rcK^|;3CH3

N- -° ct

(y cXi 0C2H5

ch3 ch3

,ch—ch2-c—ch3

nhcoch' ch3 pu i 3

e. (ch^ccochconh-^ > ^ch2ch2ch-ch2-c-ch3

ch3 ch3

.*L 0

7

GB 2 032 638 A 7

7. (ch3)3ccoch con h yy ch2—n n —^ ^

nhcoch ch3 ch3

.ch—ch2—c—ch3 ch3

ch3 I 0

"ch2ch2 ch— ch^—c— ch3

ch

3

ch3

8. (ch3)3ccochconh fl ch3

chchp c— ch*

/ \ 0

nhcoch c"3 chj xh2ch2ch-ch2-c- ch3

ch3 ch3

9 (ch3)3ccochconh

VV ct

, C6H13

nhcoch v°8h17

CH2—N

—w J

8

GB 2 032 638 A 8

10. ^ y—cochconh

.C6Hi7

/

nh-coch r\ f~\ Nc8Hl7

n

tt ™lurx ch3—N LOCH2 (ij

11. (ch3)3 ccochconh rv-(

XI

ch3 ch3 i i ch—ch2-c— ch3

nh-coch'

ch3

\ f3

xh2ch2ch-ch2-c- ch3 ch3 ch3

/

12. (ch3)3 ccochconh yt ch3-n 1 0c2h5

ch3 ch3

| I

ch—ch2-c— ch3

NHCOCH^ CH3

./

ch2ch2ch-ch2-c- ch3

ch3

ch3 c-

I

ch3

9

GB 2 032 638 A 9

13.

ch3 ch3 ch3-c—ch2— ch — ch2—ch2

ch3

ch

3

ch3—c—ch2—ch ch3 ch3

cochconh-^ ^ CI

0

CH3—N

O-C2H5

Of the compounds of the present invention, Compound 1 shown above is particularly preferable The couplers of the present invention can be synthesized according to the following reaction scheme:—

A—NO,

► A—NH,

/

-►A—NHCOCH

Ri r,

In the above formulae, A has the same meaning as defined in general formula (I).

10

15

SYNTHESIS EXAMPLE 1

Synthesis of a-pivaloyl-a-(5r5-dimethyl-2,4-dioxo-3-oxazolidinyl)-2-chloro-5-[2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctanamido]-acetanilide (coupler I):

a:~pivaloyl-a:-(5,5-dimethyl-2,4-dioxo-3-oxazolidinyl)-2-chloro-5-nitroacetanilide was refluxed with iron in aqueous isopropyl alcohol in the presence of ammonium chloride as a catalyst for 1 hour to obtain a reduced product, a-pivaloyl-a-(5,5-dimethyl-2,4-dioxo-3-oxazoildinyi)-5-am]no-2-chloroacetanilide. An acid chloride obtained by the reaction between 2-(1,3,3-tri-methyl6utyl)-5,7,7-trimethyloctanoic acid and thionyl chloride was refluxed with an equimolar amount of a-pivaloyl-a;-(5,5-dimethyl-2,4-dioxo-3-oxazolidinyl)-5-amino-2-chloroacetanilide in acetonitrile for 3 hours.

After acetonitrile was distilled off from the resulting condensation product, the oily matter thus obtained was dissolved in chloroform and washed with water. After chloroform was distilled off, recrystallization of the residue from n-hexane afforded the desired coupler having a melting point of 105 to 107°C in a yield of 75%.

10

15

20 Elemental Analysis:

Calcd.: Found:

20

H

C

N

8.52

65.28

6.34

8.42

65.33

6.24

SYNTHESIS EXAMPLE 2

25 Synthesis of a-pivaloyl-a-(5,5-dimethyl-2,4-dioxo-3-oxazolidinyl)-2-chloro-5-(2- 25

hexyldecanamido))acetanilide (coupler 2):

An acid chloride obtained by the reaction between 2-hexyldecanoicacid and thionyl chloride was refluxed with an equimolar amount of a-pivaloyl-a;-(5,5-dimethyl-2,4-dioxo-3-oxazolidinyl)-5-amino-2-chloroacetanilide obtained according to Synthesis Example 1 in acetonitrile for 3 hours. After 30 acetonitrile was distilled off from the resulting condensation product, the oily matter thus obtained was 30 dissolved in chloroform and washed with water. After the chloroform was distilled off, recrystallization of the residue from /7-hexane afforded the desired coupler having a melting point of 117 to 120°C in a yield of 70%

10

GB 2 032 638 A 10

Elemental Analysis:

J±

_C

N

Calcd.:

8.26

64.38

6.62

Found:

8.22

64.25

6.54

In the production of silver halide color photographic light-sensitive materials, the couplers of the 5 present invention may be used alone or in combination. 5

In the color photographic light-sensitive material containing the coupler of the present invention there may also be incorporated, for example, DIR couplers or DIR compounds (e.g., those described in U.S. Patents 3,632,345, 3,227,554 and 3,379,529 and Japanese Patent Applications (OPI) Nos. 122335/74, 34232/75 and 135310/75), yellow dye-forming couplers (e.g., those described in West 10 German Patent Application (OLS) No. 2,213,461 and U.S. Patents 3,510,306,3,644,498 and 10

3,894,875), magenta dye-forming couplers (e.g., those described in U.S. Patent 3,61 5,506 and West German Patent Applications (OLS) Nos. 2,418,959 and 2,424,467), or cyan dye-forming couplers (e.g.

those described in U.S. Patents 2,474,293, 3,034,892, 3,591,383, 3,311,476 and 3,476,563).

The coupler of the present invention is advantageously dispersed in a photographic emulsion in a 1 5 solution of an organic solvent. A specific example of dispersing couplers is described in detail in U.S. 15 Patent 3,676,131. The organic solvents useful for dissolving the couplers are those which are slightly soluble in water and have a high boiling point (160°C); for example, substituted hydrocarbons,

carboxylic acid esters, benzoic acid esters, citric acid esters, carboxylic acid amides, phosphoric acid esters, ethers, etc. Specific examples thereof include di-/7-butyl phthalate, n-octylbenzoate, o-acetyl 20 tributyl citrate, tricresyl phosphate, tri-/7-hexyl phosphate, N,N-diethyl-caprylamide, etc. It is 20

advantageous to use low boiling auxiliary solvents in addition to these high-boiling solvents. Examples of such solvents include propylene carbonate, ethyl acetate, butyl acetate, cyclohexanol,

tetrahydrofuran, cyclohexanone, etc.

The use of a surface active agent is advantageous for finely dispersing these solvents in a 25 hydrophilic colloid to be used as a photographic emulsion. Diffusion-resistant couplers containing in one 25 molecule thereof both a ballast group and a carboxylic or sulfonic acid group are soluble in a neutral or alkaline aqueous solution, and the solution can be added to the photographic emulsion.

The couplers are generally added to an emulsion in an amount of about 5 to 1500 g per mol of silver halide; however the amount can vary depending upon the use, with about 10 to 500 g per mol of 30 silver halide being preferable. A suitable amount of a silver halide is about 0.2 to 4 g/m2 and preferably 30 about 0.5 to 3 g/m2 (which may be \ to 1/100 of the conventional amount).

The couplers of the present invention can be applied to various color light-sensitive materials as well as various silver halide light-sensitive materials such as color negative films, color positive films,

color reversal films, color paper, etc. and are preferably located in a silver halide emulsion layer. 35 Suitable silver halide emulsions which can be used in the present invention include those 35

containing silver chloride and silver bromide as well as mixed halides of silver, such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc.

The silver halide grains of these emulsions may be of a cubic form, an octahedral form, or may have a mixed crystalline structure.

40 The silver halide grain size distribution may be narrow or broad, and is not particularly limited. 40 Suitable methods of preparing the silver halide emulsion which can be used include those well known in the art, such as the single and double jet process, the controlled double jet process, etc.

Two or more types of silver halide emulsions which have been prepared separately using different processes can be employed. The grain structure of the silver halide may be uniform or different from the 45 surface to the interior, or may be of the so-called "conversion" type as described in British Patent 45

635,841, and U.S. Patent 3,622,318.

Further, silver halide grains which provide latent images primarily at the surface thereof or in the interior can be employed in the present invention.

The silver halide emulsions used in this invention may be chemically sensitized using well-known 50 chemical sentitizers including N,N,N'-trimethylthiourea, the complex salts of monovalent gold such as 50 the thiocyanates or the thiosulfates, etc., stannous chloride, hexamethylenetetramine, etc.

Suitable hydrophilic high molecular weight materials which can be present in the photographic coatings of the present invention include gelatin, cellulose derivatives, such as carboxymethylcellulose, hydroxyethylceliulose, etc., carbohydrate derivatives, such as starch derivatives, synthetic hydrophilic 55 colloid materials, such as poly(vinyl alcohol), poly(N-vinyl-pyrrolidone), copolymers containing acrylic 55 acid, polyacrylamide and the derivatives or partially hydrolyzed products of the above described polymers, etc. Of these, the most representative is gelatin and gelatin is most generally used. The gelatin can be partly or completely replaced by a synthetic polymer or a gelatin derivative.

The couplers of the present invention are applicable to multi-layer color light-sensitive materials 60 (e.g., those described in U.S. Patents 3,726,681 and 3,516,831 and British Patents Nos. 818,687 and 60

11

GB 2 032 638 A 11

923,045) or to the process described in British Patent 1,513,321. Furthermore, they can be used together with DIR compounds described in West German Patent Application (OLS) No. 2,322,165 or U.S. Patent 3,703,375).

The light-sensitive material to be used for the present invention may contain, in an emulsion layer 5 or a neighboring layer, a p-substituted phenol derivative such as a hydroquinone derivative, which is advantageous for stabilizing color images. Particularly effective p-substituted phenol derivatives such as 6,6'-Dihydroxy-4,4,7,4',4',7'-hexamethyl-2,2'-bis-spirochromane are those described in U.S. Patents 2,360,290, 3,418,613, 2,675,314, 2,710,801,2,728,659, 2,732,300, 2,735,765, 2,816,028, 3,609,262, 3,432,300, 3,457,079, 3,573,050, 3,574,627 and 3,764,337, Japanese Patent 10 Publication No. 13496/68 and Japanese Patent Application (OPI) No. 4738/72.

The light-sensitive material containing the coupler of the present invention may contain in an emulsion layer or a neighbouring layer an ultraviolet absorbing agent such as 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole described in, for example, U.S. Patents 3,250,617 and 3,253,921 for stabilization of images.

15 The couplers of the present invention can also be applied to low-silver content light-sensitive materials containing approximately 1/2 to 1/100 the silver in conventional emulsions. With such color light-sensitive materials containing a reduced amount of silver halide, adequate image densities can be obtained according to, for example, image-forming processes for increasing the amount of dye produced utilizing color intensification with peroxide, cobalt complexes, or sodium chlorite (described in, 20 for example, West German Patent Application (OLS) No. 2,357,694, U.S. Patents 3,674,490,

3,761,265, 4,002,477, 3,970,458, 3,923,511, 3,856,524, 3,862,842, 3,826,652, 3,834,907 and 3,765,891 and West German Patent Applications (OLS) Nos. 2,044,833, 2,056,359, 2,056,360 and 2,226,770.

The color photographic material of the present invention can be subjected to conventional and 25 well known processings comprising, after exposure, color development, bleaching and fixing. Each processing step may be combined with another using a processing agent capable of accomplishing the corresponding functions. A typical example of such a combined processing is a mono-bath process using a blix.

Depending on the requirements, the development processing can include additional steps such as 30 pre-hardening, neutralization, primary development (black-and-white development), image stabilization, washing with water, etc. The processing temperature, which is determined depending on the kind of photographic material as well as by the processing composition, is sometimes below about 18°C but, in most cases, is not lower than 18°C.

A particularly useful temperature range is from about 20 to 60°C. The temperature may be varied 35 from one processing step to another in the processing.

A color developer comprises an aqueous alkaline solution with a pH not lower than about 8, and more preferably between 9 and 12, containing a color developing agent the oxidation product of which is capable of reacting with a coupler to form a dye.

Suitable color developing agents which can be used include, for example, 4-amine-N,N-40 diethylamide, 3-methyl-4-amino-N,N-diethylaniiine, 4-amino-N-ethyl-N-/5-hydroxyethylaniline, 3-methyl-4-amino-N~ethyl-N-/3-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-/3-methanesulfamidoethylaniline, 4-amino-N,N-dimethylaniline, 4-amino-3-methoxy-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-/5-methoxyethylaniline, 4-amino-3-methoxy-N-ethyl-N-/3-methoxyethylaniline, 4-amino-3-/3-methanesulfamidoethyl-N,N-diethylaniline, and the salts thereof, 45 such as the sulfates, the hydrochlorides, the sulfites, the p-toluenesulfonates, etc. Other color developing agents which can be used are described in U.S. Patents 2,592,364 and 2,193,015,

Japanese Patent Application (OPI) No. 64933/73, and L. E. A. Mason, Photographic Processing Chemistry, pp 226—229, Focal Press, London (1966).

Each of the above-described compounds can be used in conjunction with 3-pyrazolidone 50 derivatives. Further, a number of additives well-known in the art may be present in the color developer.

The coupler used in this invention can also be incorporated into the color developer and a suitable amount of the coupler of this invention which can be used in the color developing solution is about 0.5 to 20 g per liter of the developing solution.

The photographic material of the present invention is subjected to bleaching after color 55 development. This step may be combined with fixing, whereby the processing solution contains a fixing agent in addition to a bleaching agent.

Suitable bleaching agents include ferricyanide salts, bichromate salts, water-soluble cobalt (III) salts, water-soluble copper (II) salts, water-soluble quinones, nitrosophenol, polyvalent metal compounds containing Fe(lil), Co(lil), Cu(ll), with complex salts of such metals with organic acids, such as, for 60 example, ethylenediamine tetraacetic acid, nitrilotriacetic acid, imidoacetic acid, N-

hydroxyethylethylenediaminetriacetic acid and other aminopolycarboxylic acids, malonic acid, tartaric acid, malic acid, digylcolic acid, dithioglycolic acid and 2,6-dipicolic acid copper complex salt, etc., being particularly preferred, peracids, such as alkyl peracids, persulfates, permanganates, hydrogen peroxide, etc., hypochlorites, etc.

65 Other additives, such as bleach accelerating agents as disclosed in U.S. Patents 3,042,520 and

5

10

15

20

25

30

35

40

45

50

55

60

65

12

GB 2 032 638 A 12

3,241,966 and Japanese Patent Publications Nos. 8506/70 and 8836/70 can be further added to the bleaching solution.

The color photographic material of the present invention will be illustrated by reference to the following example.

5 EXAMPLE 5

A solution prepared by heating 27 g of the aforesaid Coupler (1) and as coupler solvents 13.5 ml of dioctylbutyl phosphate and 50 ml of ethyl acetate at 70°C was added to 300 ml of an aqueous solution containing 50 g of gelatin and 2.0 g of sodium dodecylbenzenesulfonate, and stirred, followed by preheating and passing five times through a colloid mill. Thus, the coupler was finely emulsified and 10 dispersed together with the solvents. 10

The whole of the resulting emulsion dispersion was added to 1.0 kg of a photographic emulsion containing 54 g of silver bromoiodide and 60 g of gelatin and, after the addition of 30 ml of a 5 %

acetone solution of triethylene phosphamide as a hardener, the pH of the resulting mixture was adjusted to 6.0, followed by coating it on a cellulose triacetate film base in a dry thickness of 7.0 fi to obtain 15 sample A. 15

In a manner analogous to the above procedure except for using 27 g each of Coupler (2), Coupler (11), Comparative Coupler (A) and Comparative Coupler (B) in place of above-described Coupler (1),

there were obtained samples B, C, D, and E.

These films were subjected to stepwise exposure for sensitometry, then to the following 20 processings: 20

Color Developing Steps:

1.

Color development processing

30°C

4 min.

2.

Bleach-fixing

30°C

2 min.

3.

Washing

30°C

2 min.

25 4.

Stabilizing bath

30°C

2 min.

25

The processing solutions used in the color development steps were respectively as follows:

*

Color Developer:

Sodium Metaborate

25

g

Sodium Sulfite

2

g

30

Hydroxylamine (sulfate)

2

g

30

Potassium Bromide

0.5

g

6-Nitrobenzimidazole (sulfate)

0.02 g

Sodium Hydroxide

4

g

Benzyl Alcohol

15.8 ml

35

Diethylene Glycol

20

ml

35

4-(N-Ethyl-N-/3-methanesulfonamido-ethyl)amino-2-methylaniline sesqui-sulfate

8

g

40

Water to make

1

liter

(pH:10.2)

40

13

GB 2 032 638 A 13

10

Bleach-Fixing Solution:

Iron (II) Ethylenediaminetetra-acetate

Ammonium Thiocyanate Sodium Sulfate

Ammonium Thiosulfate (60 % by weight aqueous solution)

Sodium Ethylenediaminetetraacetate

Water to make

45 g

10 %

10 g

100 ml 5 g liter (pH: 6.9)

10

Stabilizing Bath:

Tartaric Acid

15

Zinc Sulfate Sodium Metaborate Water to make

10 g • 10 g

20 g liter

15

20

The thus obtained developed films were subjected to the tests for stability to light. Samples were placed in a xenon testing apparatus to expose to 2.5 x 106 lux.hr light for 8 days. Then, the percentage of reduction in yellow color density of the light-exposed samples and of the unexposed samples were compared.

Table 1 shows the results of the measurement of percentages of reduction in color density of color 20 images at initial densities of 0.50 and 1.50.

Comparative Coupler (A) and (B) have the following structural formulae, respectively:

(A)

(B)

14

GB 2 032 638 A 14

Table 1

Percentage of Reduction in color Density

Sample

Coupler

Initial Density

0.5

1.5

A

(1)

18

15

B

(2)

27

21

C

(11)

19

17

D

A

50

43

E

B

51

41

As is clear from the results in Table 1, Samples A, B and C using the compounds of the present invention suffered less fading with light as compared with comparative samples D and E.

Claims

5 1. A silver halide color photographic material having a layer containing a yellow-forming coupler represented by the following general formula:

A—NHC— CH

i! \

0 r2

wherein A represents a molecule of a yellow coupler from which one hydrogen atom bound to a carbon atom other than at a coupling position is removed, and r, and r2 each represents an alkyl group 10 containing 2 to 16 carbon atoms, the sum of the carbon atoms contained in r, and r2 being 10 to 20. 10

2. A photographic material as claimed in Claim 1, wherein A is derived from a coupler represented by the formula:

R,—C—CH—C—NHR4 (II)

II I J oxo wherein R3 represents an optionally substituted aliphatic, aromatic or heterocylic group, R4 represents 15 an optionally substituted aromatic or heterocyclic group and X is represented by one of the following 15 formulae:

y"v ^ n"^5

(n) W (r)

wherein Z represents the non-metallic atoms necessary to complete a 4-, 5- or 6-membered ring, R represents an aryl group or a heterocyclic group and Rs and R6 each represents a hydrogen atom, a 20 halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an 20

15

GB 2 032 638 A 15

alkoxy group, an alkylsulfoxy, an acyl group, a sulfonyl group, a substituted or unsubstituted phenyl group or a heterocyclic group.

3. A color photographic material as claimed in Claim 2, wherein X is represented by one of the following formulae (VI)—(IX):

O N. ^

*r

■n

-X,

*r x2

t

*2

°YnY°

X4-N N—X5

(2c) w (m) (21)

wherein X, and X2 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, X3, X4 and X5 each represents a hydrogen atom, an alkyl group, an aryl group, an araTkyl group or an acyl group, W represents an oxygen atom or a sulfur atom and X6 represents a monovalent substitutent.

4. A color photographic material as claimed in Claim 1, wherein said coupler is represented by the 10 formula h-

ch-

■nh

nhcch

0

'Ri

R 2

wherein Rv R2, R3 and X are as defined in Claim 2 or 3 and Y represents a halogen atom or an alkoxy group.

15 5. A color photographic material as claimed in any preceding claim, wherein said coupler is any of 15

the Couplers 1 to 12 shown hereinbefore.

6. A color photographic material as claimed in any preceding cl-aim, wherein said coupler is present in an amount of 5 to 1500 grams per mol of silver halide.

7. A color photographic material as claimed in Claim 6, wherein said coupler is present in an

20 amount of 10 to 500 grams per mol of silver halide. 20

8. A color photographic material as claimed in any preceding claim, wherein said material is a color negative film, a color positive film, a color reversal film or a color paper.

9. A color photographic material as claimed in any preceding claim, wherein said silver halide is present in an amount of 0.5 to 3 grams per square metre of the material.

25 10. A color photographic material as claimed in any preceding claim, wherein said coupler is 25 located in a silver halide emulsion layer.

11. A color photographic material as claimed in Claim 10, wherein said silver halide emulsion layer or an adjacent layer contains a p-substituted phenol derivative.

12. A color photographic material as claimed in Claim 1, substantially as hereinbefore described

30 with reference to Sample A, B or C of the Example. 30

13. An aqueous alkaline color developer solution which contains a color developing agent and a yellow-forming coupler as defined in any of Claims 1 to 5.

14. A color photograph containing a yellow dye formed by imagewise exposure and color development of a silver halide photographic material as defined in any of Claims 1 to 12 or by use of a

35 color developer solution as claimed in Claim 13. 35

Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.